Sulphuric acid esters of alcohols and derivatives thereof



Patented Oct. 24, 1933 UNITED STATES PATENT OFFICE SULPHURIC ACID ESTERS OF' ALCOHOLS AND DERIVATIVES THEREOF Karl Marx, Karl Br odersen, and Matthias Quaedvlieg, Dessau in Anhalt, Germany, as-' signers, by mesne assignments, to I. G. Farbenindustrie A. G., ,Germany, a corporati Frankfort-on-the-Main, on of Germany No Drawing. Application August 17, 1931, Serial No. 557,734, and in Germany August 21, 1930.

Renewed July 15, 1933 14 Claims.

Our present invention relates to a new process for manufacturing sulphuric acid esters of alcohols and the derivatives thereof.

The products obtainable according to this invention correspond to the general formula wherein R means an alkyl or aralkyl radical containing at least 10 carbon atoms and X stands for H or a salt forming inorganic or organic compound, such as alkali metal, ammonium, or the group H-NH2 Y, Y meaning phenyl, tolyl, naphthyl, CONH-z,

and similar radicals.

We have found that alcoholic compounds having in their molecule more than 10 carbon atoms, are easily transformed into the corresponding sulphuric acid esters by acting upon them with aminosulphonic acid or the derivatives thereof. The formation of sulphuric acid esters occurs with these agents in a very smooth manner and the esters are obtainable in a very good yield and in a sufiiciently pure state;

As alcoholic substances with more than 10 carbon atoms which may be used as starting materials we enumerate the followingz-the higher aliphatic alcohols such as, for instance, dodecyl said compounds, the compound may be reacted with the free aminosulphonic acid. In this case the reaction occurs according to the following equation:

As compared with the usual method of preparing sulphuric acid esters, the process according to our present invention involves the advantage that the neutral ammonium salt of the sulphuric acid ester is produced directly and that a further treatment is no longer necessary.

The aminosulphonic acid may be employed, either partially or wholly in form of a salt,

. especially with an organic base, such as pyridine.

The amount of the base present in the esterifying mixture, may vary within wide limits. Thus, an excess of base may, for instance, be used as a solvent; it is, however, advantageous to use only very small quantities of the base, which are already suflicient to accelerate the reaction.

Instead of the aminosulphonic acid there may likewise be used organic sulphamic acids, such as HO3S--NHCONH2, phenyl and tolyl sulphamic acid and the salts thereof, for instance, of the alkalies, of ammonium or of organic bases. In this manner, salts are obtained of the sulphuric acid ester and the bases from which the sulphamic acids are derived. The reaction probably occurs according to the following equation:

alcohol,:-hexadecyl alcohol, octadecyl alcohol,-

polyvalentfalcohols with more than 10 carbon or a cyclohexyl group, alcohols corresponding to the general formula R,CO--NHROH (R meaning. a higher. aliphatic radical and R an aliphatic radical) such, aslauroyl-hydrxyethylamide,;the hydroxyethyl: or propyl amide of coconutoilacid, stearoylhydroxypropyl amide, mono- GB-ltboxylicacids esters ofthe higher fatty acids, such-as esters of coconut oil acid, oleic acid,

, stearic acid, palmitic acid with polyvalent alcohols such as glycerin, sorbit and polyglycerin,

and mono-ethers of polyvalent alcohols, such as stearyl-glycerin ether, palmitylglycerin ether.

For preparing the sulphuric acid esters of the The following examples illustrate the invention:

Example 2.100 parts of an alcohol mixture (having the average molecular weight 175) obtained by theoxidation of paraffin are heated for 4 hours to 100 C.-110 C.Twhile well stirring, with 56 parts of aminosulphonic acid. The product obtained is a mass of the'nature of an ointment which dissolves in water to a clear solution.

Example 3.270 parts of stearyl alcohol are stirred at 110 C. for some hours with 180 parts of 4-methylphenylsulphamic acid. There are ob tained 450 parts of a product which dissolvesv in water to a clear solution and solidifies in the cold to a waxlike mass.

Example 4.270 parts of stearyl alcohol are mixed at 100 C., while stirring, with 350 parts of benzamide-N-sulphonate of benzamide. The

. temperature is kept for about hour at 100 C.

110 C. The reaction probably takes place according to the following equation:

physiologische Chemie, vol. 146, pages 227-240) The reaction probably occurs according to the following equation: 4

' In an' analogous manner" the glycolmonocetyl ether can easily be convfied into its surphuric acid ester. The pyridini salt formed maybe converted into the sodium salt by addition of caustic soda.

Example 8.40 parts of coconut fatty acid hydroxyethyl amide are heated in a reflux apparatus for 2 to 3 hours, while stirring, with 32 parts of aminosulphonic acid and 30 parts of 1.2-dichlorethane. Instead of 1.2-dich1orethane other solvents may also be used, for instance, carbon tetrachloride, trichlorethylene, benzene or the like. After the reaction is complete, 50 parts of water are added and then the quantity of a concentrated caustic soda solution which is required for the conversion of the product into the sodium salt. The solvent and the ammonia evolved are removed simultaneously by distillation. The sodium salt of the sulphuric acid ester of the coconut fatty acid-hydroxyethylamide remains in the form of a white paste having the consistency of soft soap. It is an excellent emulsifying, agent and a detergent of good qualities even in hard or acid water.

Since the benzamide salt obtained is hydrolyzed in the presence of water, the clear melt is dissolved in 3500 parts of hot water and the solution is Example 9.100 parts of lauroyl-hydroxyethylamide are stirred for 4 hours with 45 parts of 5 is soluble in water and solidifies in the cold to a mixed with a sodium hydroxide solution until the j Sulphmic i at a tempera? abmft reaction is weakly alumna The whole is then 85 C. The ammonium salt of the acid sulphomc cooled to 40 C. and the benzamide is eliminated acid ester thus obtained, is converted into the soy fil ti n h fi ate is then evaporated. dium salt by addition of caustic soda. This prod- Example 5.-270 parts of stearyl alcohol are stirred for some hours at 110 C. with 200 parts of the arh onium salt of paratoluidinesulphamic agent for fabncs artlficlal 511k and so acid. The reaction probably occurs according to Example 1o-28 Parts of Phenylbutanol, the following equation: parts of the ammonium salt of the iminodisul- About 460 parts of a product are obtained which phonic acid of the following constitution:

503NH waxllke mass.

Example 6.150 parts of stearyl alcohol are NH heated to 110 C.-120 0., while stirring, with somn.

parts of aminosulphonic acid and 5 parts of pyridine. The reaction is already complete after 0111i; hfiikil', whereasul 1n hthe absecriultle 0tf' thefpy1d distilling the pyridine in excess under reduced hgurs a gfii gz g gg g g A ff f 2 3 :2 pressure, a salt of the phenyl-butylsulphuric acid ta-ined,if insteadof pyridine corresponding quanfi i if the salt other titles of ethylolamine, dipropylolamine, triethylfor ms t ose i g 185 or of olamine, diethylaniline or other bases were used. game bases can used wlt gsame p Example parts of 1auroyl hy dmxyethy1 Example 11 .40 parts of a mixture of primary,

and 200 parts of pyridine are heated to boiling for about 8 hours in a reflux apparatus. After amide parts of pyridine and 9 parts of ammo secondary and tertiary alcohols (average molecusuphonic acid are heated, while stirring, for 3 lar weight 195) obtainefi by oxidizirfg a hours to C.-100 C. The pyridine in excess is 55 P511175 9 the ammomllm Salt 9 nflmodlsul' then removed, for instance,- by distillation. The phomc and or the ionowmg constltutmn:

sulphuric acid ester of the lauroyl hydroxyethyl- BOJNHI amide is obtained which could hitherto notbe N NH: obtained in a pure form, since during sulphonatso NH ing with sulphuric acid the lauroyl group is displaced to the hydroxyl grouy (cf. Zeitschrift fiir and 200 parts of pyridine are heated to boiling,

not has outstanding good qualities as a softening while stirring, for 8 hours in a reflux apparatus. 1 The product is worked up as indicated in Example 10. The ammonium salts of the corresponding sulphuric acid esters are thus obtained in the 5 form of a semi-solid and water-soluble mass.

Example 12.-24 parts of cetyl alcohol, 27 parts of ammonium iminodisulphonate of the follow-- ing constitution:

and 100 parts of pyridine are-heated to boiling, while stirring, for 10 hours in a reflux apparatus. The mass obtained is worked up as indicated in Example 10. There is obtained the ammonium salt of the cetylsulphuric acid. The cetyl alcohol can also be replaced by equivalent quantities of a cetyl alcohol substituted, for instance, by C1 01' 0001-15.

What we claim is:- 1. The process which comprises acting upon a compound having an aliphatic alcoholic group and at least 10 carbon atoms with a sul'phonating agent of the group consisting of amino sulphonic acid, aminosulphonates, organic sulphamic acids, alkali metal-, ammonium salts and salts of organic bases of organic sulphamic acids, and iminoclisulphonic acid salts.

2. The process which comprises acting upon a compound having an aliphatic alcoholic group and at least 10 carbon atoms with a sulphonating agent oi the group consisting of amino sulphonic acid,amino-sulphonates, organic sulphamic acids, alkali metal-', ammonium salts and salts of organic bases of organic sulphamic acids and iminodisulphonic acid salts in the presence ofa, nitrogenous organic base.

3. The process which comprises acting upon a compound having an aliphatic alcoholic group. and at least 10 carbon atoms with amino sulphoni'c-- acid in the presence of a nitrogenous organic base and converting the ammonium salt formed into the corresponding sodium salt by addition of caustic soda.

4. The process which comprises acting upon a higher fatty acid hydroxy alkyl amide with a sulphonating agentof the group consisting of aminosulphonic acid, aminosulphonates, organic sulphamic acids, alkali metal-, ammonium salts,

and salts of organic bases of organic sulphamic acids, and iminodisulphonic acid salts.

5. The process which comprises acting upon a higher fatty acid hydroxyalkyl amide with a sulphonatlng agent. of the group consisting of aminosulphonic acid, aminosulphonates, organic sulphamic acids, alkali metal-, ammonium'salts and salts of organic bases of organic sulphamic acids, and iminodisulphonic acid salts in the and iminodisulphonlc acid salts in the presence of a nitrogenous organic base.

7. The process which comprises acting upo lauroyl hydromethyl amide with aminosulphonic acid at a temperature of about 85 C.

8. The process which comprises acting upon lauroyl hydroxyethyl amide with aminosulphonic acid at a temperature of about -100 C. in the presence of pyridine.

9. The process which. comprises acting upon lauroyl hydroxyethyl amide with aminosulphonic acid at a temperature of about C. and converting the ammonium salt formed into the corresponding sodium salt by addition of caustic soda.

10. The process which comprises acting upon coconut oil acid hydroxyethyl amide in the heat with aminosulphonic acid in the presence of an organic solvent.

11. As new products the compounds corre= spending to the general formula wherein R means the radical of an aliphatic hydrocarbon containing at least 10 carbon atoms, R means an alkylene radical, and X ends for an alkali metal, ammonium or H bound to a nitrogenous organic base, said products being soaplike substances soluble in water, having good emulsifying and washing properties and being softening agents for fabrics and artificial silk.

12. As new products the compounds corresponding to the general formula cuH -coNn cH2crnos03x,

wherein X means an alkali metal or ammonium, said products being soap-like substances soluble in water, having good emulsifying and washing properties and being softening agents for labrics and artificial silk.

13.As new products the compounds corre-.

spondlng to the general formula R-CONH-ROSOaX wherein R means an alkylene radical and X stands for an alkali metal, ammonium or H bound to a nitrogenous organic base, said products being soap-like substances soluble in water, having good emulsifying and washing properties and being softening agents for fabrics and artificial silk.

KARL MARX. KARL BRODERSEN. MA'I'IHIAS QUAEDVLIEG. 

